Crystal supramolecularity:: sixfold phenyl embraces between PPh3 ligands, forming extended nets in one-, two-, and three-dimensions

The sixfold phenyl embrace (6PE) is manifest in the crystal structures of approximately 30% of the 5089 molecules with PPh3 ligands (in the Cambridge Structural Database). This paper describes the characteristics and occurrence of the 6PE as a crystal supramolecular motif between metal complexes and clusters with PPh3 ligands. The number of PPh3 ligands per molecule, the coordination stereochemistry, and possible crowding of the PPh3 ligands are included in the analysis. Molecules with multiple PPh3 ligands can and do form one-, two-, and three-dimensional supramolecular networks constructed with these multiple phenyl embraces. We portray a representative selection of the resulting tectonic lattices based on 6PEs. Variants on the 6PE include a pseudo-embrace in which gold takes the place of a phenyl ring.